Copper DOC316.53.

01038

Porphyrin Method1 Method 8143

1 to 210 µg/L Cu (LR) Powder Pillows
Scope and application: For water, wastewater and seawater.
1 Adapted from Ishii and Koh, Bunseki Kagaku, 28 (473), 1979.

Test preparation

Instrument-specific information
Table 1 shows all of the instruments that have the program for this test. The table also
shows sample cell and orientation requirements for reagent addition tests, such as
powder pillow or bulk reagent tests.
To use the table, select an instrument, then read across to find the applicable information
for this test.
Table 1 Instrument-specific information
Instrument Sample cell orientation Sample cell
DR 6000 The fill line is to the right. 2495402
DR 3800
DR 2800
DR 2700
DR 1900
DR 5000 The fill line is toward the user.
DR 3900
DR 900 The orientation mark is toward the user. 2401906

Before starting
Install the instrument cap on the DR 900 cell holder before ZERO or READ is pushed.
To make sure that all forms of the metal are measured, digest the sample with heat and acid. Use the mild or vigorous
digestion. Refer to the Water Analysis Guide for more information.
Wash all glassware with detergent. Rinse with tap water. Rinse again with 1:1 nitric acid solution. Rinse a third time with
high-quality deionized water. These steps will remove deposits that can cause slightly high results.
If samples contain high levels of metals, a slight metallic deposit or yellow buildup may form in the sample cell. Wash the cell
as described above.
For the best results, measure the reagent blank value for each new lot of reagent. Replace the sample with deionized water
in the test procedure to determine the reagent blank value. Subtract the reagent blank value from the sample results
automatically with the reagent blank adjust option.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

1
Items to collect
Description Quantity

Copper Masking Reagent Powder Pillows, 10-mL 1

Porphyrin 1 Reagent Powder Pillows, 10-mL 2
Porphyrin 2 Reagent Powder Pillows, 10-mL 2
Nitric Acid Solution, 1:1 varies
Sample cells (For information about sample cells, adapters or light shields, refer to Instrument-
2
specific information on page 1.)

Refer to Consumables and replacement items on page 5 for order information.

Sample collection and storage

• Collect samples in clean glass or plastic bottles that have been cleaned with 6 N (1:1)
hydrochloric acid and rinsed with deionized water.
• To preserve samples for later analysis, adjust the sample pH to less than 2 with
concentrated nitric acid (approximately 2 mL per liter). No acid addition is necessary if
the sample is tested immediately.
• Keep the preserved samples at room temperature for a maximum of 6 months.
• Before analysis, adjust the pH to 2–6 with 5 N sodium hydroxide solution.
• Correct the test result for the dilution caused by the volume additions.

Powder pillow procedure

Start

1. Start program 145 2. Prepare the blank: Fill 3. Add the contents of one 4. Swirl to dissolve the
Copper, Porphyrin. For the sample cell with 10 mL Copper Masking Reagent reagent.
information about sample of sample. powder pillow.
cells, adapters or light
shields, refer to Instrument-
specific information
on page 1.
Note: Although the program
name can be different
between instruments, the
program number does not
change.

2 Copper, Porphyrin Method (210 µg/L)

5. Prepare the sample: Fill
a second sample cell with
10 mL of sample.
9. Swirl to mix.
If copper is present in the
sample, the sample will
show blue, then go back to
a yellow color.
Zero
13. Push ZERO. The
display shows 0 µg/L Cu.
Interferences
Interfering substance
Aluminum, Al3+
Cadmium, Cd2+
Calcium, Ca2+
Chelating agents
Chloride, Cl-
Chromium, Cr6+
Copper, Porphyrin Method (210 µg/L)
6. Add the contents of one 7. Swirl to mix. 8. Add the contents of one
Porphyrin 1 Reagent Porphyrin 2 Reagent
Powder Pillow to each Powder Pillow to each
sample cell. sample cell.
10. Start the instrument 11. When the timer expires, 12. Insert the blank into the
timer. A 3-minute reaction clean the blank sample cell. cell holder.
time starts.
Read
14. Clean the prepared 15. Insert the prepared 16. Push READ. Results
sample cell. sample into the cell holder. show in µg/L Cu.
Interference level
60 mg/L
10 mg/L
1500 mg/L
Interfere at all levels unless either the Digesdahl or vigorous digestion is
completed.
90,000 mg/L
110 mg/L
3
Interfering substance Interference level
Cobalt, Co2+ 100 mg/L
Fluoride, F- 30,000 mg/L
Iron, Fe2+ 6 mg/L
Lead, Pb2+ 3 mg/L
Magnesium 10,000 mg/L
Manganese 140 mg/L
Mercury, Hg2+ 3 mg/L
Molybdenum 11 mg/L
Nickel, Ni2+ 60 mg/L
Potassium, K+ 60,000 mg/L
Sodium, Na+ 90,000 mg/L
Zinc, Zn2+ 9 mg/L
Highly buffered samples or extreme sample pH Can prevent the correct pH adjustment of the sample by the reagents.
Sample pre-treatment may be necessary.

Accuracy check
Standard additions method (sample spike)
Use the standard additions method (for applicable instruments) to validate the test
procedure, reagents and instrument and to find if there is an interference in the sample.
Items to collect:
• Copper Standard Solution, 4 mg/L (PourRite® Ampule or prepare from a dilution of a
higher concentration copper standard solution)
• Ampule breaker
• Pipet, TenSette®, 0.1–1.0 mL and tips

1. Use the test procedure to measure the concentration of the sample, then keep the
(unspiked) sample in the instrument.
2. Go to the Standard Additions option in the instrument menu.
3. Select the values for standard concentration, sample volume and spike volumes.
4. Open the standard solution.
5. Prepare six spiked 10-mL samples: use the TenSette pipet to add 0.1 mL, 0.2 mL and
0.3 mL of the standard solution, respectively, to two 10-mL portions of fresh sample.
Mix well.
6. Use the test procedure to measure the concentration of each of the spiked samples.
Start with the smallest sample spike. Measure each of the spiked samples in the
instrument.
7. Select Graph to compare the expected results to the actual results.
Note: If the actual results are significantly different from the expected results, make sure that
the sample volumes and sample spikes are measured accurately. The sample volumes and
sample spikes that are used should agree with the selections in the standard additions menu. If
the results are not within acceptable limits, the sample may contain an interference.

Standard solution method

Use the standard solution method to validate the test procedure, the reagents and the
instrument.
Items to collect:
• Copper Standard Solution, 10 mg/L
• 1000-mL volumetric flask, Class A

4 Copper, Porphyrin Method (210 µg/L)

 • 15-mL volumetric pipet, Class A and pipet filler
• Deionized water

1. Prepare a 150 µg/L copper standard solution as follows:

a. Use a pipet to add 15.00 mL of 10-mg/L copper standard solution into the
volumetric flask.
b. Dilute to the mark with deionized water. Mix well. Prepare this solution daily.
2. Use the test procedure to measure the concentration of the prepared standard
solution.
3. Compare the expected result to the actual result.
Note: The factory calibration can be adjusted slightly with the standard adjust option so that the
instrument shows the expected value of the standard solution. The adjusted calibration is then
used for all test results. This adjustment can increase the test accuracy when there are slight
variations in the reagents or instruments.

Method performance
The method performance data that follows was derived from laboratory tests that were
measured on a spectrophotometer during ideal test conditions. Users can get different
results under different test conditions.
Program Standard Precision (95% confidence interval) Sensitivity
Concentration change per 0.010 Abs change
145 50 µg/L Cu 47–53 µg/L Cu 1 µg/L Cu

Summary of method
The porphyrin method is very sensitive to trace amounts of free copper. The method is
free from most interferences and does not require any sample extraction or concentration
before analysis. Interferences from other metals are removed with the copper masking
reagent. The porphyrin indicator forms an intense, yellow-colored complex with any free
copper present in sample. The measurement wavelength is 425 nm for
spectrophotometers or 420 nm for colorimeters.
Consumables and replacement items
Required reagents and apparatus

Description Quantity/test Unit Item no.

Nitric Acid Solution, 1:1 varies 500 mL 254049

Copper Reagent Set, Porphyrin, 10-mL 1 100/pkg 2603300
Includes:
Copper Masking Reagent Powder Pillow, 10-mL 1 100/pkg 2603449
Porphyrin 1 Reagent Powder Pillow, 10-mL 2 100/pkg 2603549
Porphyrin 2 Reagent Powder Pillow, 10-mL 2 100/pkg 2603649

Recommended standards

Description Unit Item no.

Copper Standard Solution, 4-mg/L, 2 mL Pour-Rite Ampules 20/pkg 2605720

Copper Standard Solution, 10-mg/L Cu 100 mL 12932
Water, deionized 4L 27256

Copper, Porphyrin Method (210 µg/L) 5

Optional reagents and apparatus

Description Unit Item no.

Sodium Hydroxide Standard Solution, 5.0 N 100 mL MDB 245032

®
Pipet, TenSette , 0.1–1.0 mL each 1970001
®
Pipet tips for TenSette Pipet, 0.1–1.0 mL 50/pkg 2185696
Pipet, volumetric Class A, 15-mL each 1451539
Flask, volumetric, Class A, 1000-mL glass each 1457453
Pipet filler, safety bulb each 1465100
Sample cells, 1" square matched set 8/pkg 2495408
Paper, pH, 0–14 pH range 100/pkg 2601300

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY

In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – techhelp@hach.com FAX: (970) 669-2932

© Hach Company/Hach Lange GmbH, 1989–2014. All rights reserved. 01/2014, Edition 9